CN103436559B - Biogas preparation method for jointly producing hydrogen and methane by carrying out enzymolysis on high-fiber aquatic plant - Google Patents
Biogas preparation method for jointly producing hydrogen and methane by carrying out enzymolysis on high-fiber aquatic plant Download PDFInfo
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- CN103436559B CN103436559B CN201310399780.7A CN201310399780A CN103436559B CN 103436559 B CN103436559 B CN 103436559B CN 201310399780 A CN201310399780 A CN 201310399780A CN 103436559 B CN103436559 B CN 103436559B
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Abstract
The invention discloses a biogas preparation method for jointly producing hydrogen and methane by carrying out enzymolysis on high-fiber aquatic plants, and belongs to the technical field of biological energy. The method comprises the following steps of: dredging and transferring massively propagated submerged plants caused by the eutrophication of a water body; carrying out enzymolysis pretreatment on a degrading enzyme, then using the obtained product as a fermentation substrate, and mixing the fermentation substrate with anaerobic active sludge; regulating the reaction condition of a reaction process through an anaerobic biological fermentation mode to achieve that the methane is generated after the hydrogen is generated so as to realize hydrogen-methane joint production; recovering biomass energy contained in solid organic matters in a biogas form. The biogas preparation method disclosed by the invention can be used for achieving the high-valued utilization of organic wastes, realizing the target of emission reduction productivity and jointly carrying out renewable resource utilization, pollution control and biological energy preparation and has the advantages of important environment benefit and wide application prospect.
Description
Technical field
The invention belongs to bioenergy technical field, relate to the novel process of a kind of enzymolysis co-producing hydrogen and methane, be specifically related to a kind of biological flue gas preparation method adopting high microsteping waterplant enzymolysis co-producing hydrogen and methane.
Background technology
Due to the impact of human being's production and life, a large amount of nitrogen, phosphorus recycling run off through farmland water-break, trade effluent, sanitary sewage and earth's surface and are input to lake, reservoir and river course, cause day by day serious body eutrophication.With in the plant-type lake of aquatic macrophyte response type, various submerged plant excess growth, defines great primary productivity, and its cover degree of communities can reach 100%, and maximum biomass (fresh weight) is 22.5kg/m
2above, they fill Water space, destroy natural landscape, and harm fish production, causes secondary pollution to water body after the corruption that sinks, also form strong biology simultaneously and urge silt effect, cause the rapid paludification of plant-type lake.According to investigations, Ulansuhai Nur, Lake Hasuhai, Hongshan Reservoir, Yi Huta lake, Yuqiao Reservoir, different Long Hu, Nansi Lake, East Taihu Lake, Lake Gucheng, Dian Chi, Erhai, Chi Hu, Baoan Lake, every lake etc. all in the impact that there is this respect in varying degrees.
Submerged plant to have from water at growing period and absorbs the ability with enrichment nutritive salt in substrate, and results submerged plant can make nitrogen in lake, the build-up effect of phosphorus recycling is inhibited, and reduces biology and fill and lead up effect.At present, in the world " controlling the approach of lake trophic status by controlling nutritive salt " is reached common understanding, therefore gather in submerged plant by mechanized manner, in geochemistry material cycle, shift the gordian technique that nitrogen, phosphorus recycling have become plant-type lake eutrophication control.
The submerged plant resource of plant-type lake is a unemployed great wealth, is the Resources of Aquatic Plants of Sustainable Development and Utilization.Such as Ulansuhai Nur submerged plant turnout 8.5 × 10
4ta
-1(dry weight), to gather in 60% calculating, can develop 5 × 10 every year
4t (dry weight) Resources of Aquatic Plants.Adopt bio anaerobic fermentation technique waterplant to be converted into the green bio energy---the hydrogen with high added value, the end products of anaerobic hydrogen-generating is utilized by methanogen further and produces methane combustion gas, realizes the coproduction of hydrogen and methane.
At present, day by day serious in energy shortage and environmental pollution, exploitation fungible energy source becomes one of focus that countries in the world government and scientist pay close attention to.Many scholars have carried out extensive research to diphasic anaerobic simultaneous hydrogen production, methane phase method process organic waste water or organic solid waste process.Have bibliographical information, hydrogen and methane blended can reduce the discharge of oxynitride etc. as fuel.Compared with homogenous anaerobic process, different dominant microflora sortings in two-phase, and is kept the stable of flora in two-phase by diphasic anaerobic process, and make product hydrogen acid-producing bacteria mainly maintain the first stage, methanogen mainly maintains subordinate phase.Two step co-producing hydrogen and methane technologies, can continue on the one hand to reduce the organic content in waste, can produce CO again on the other hand
2as energy gas, the energy conversion rate of whole fermenting process significantly being improved, is a kind of desirable turning waste into wealth, eco-friendly energy technique.
Therefore, research and develop the biological flue gas preparation method of co-producing hydrogen and methane after a kind of Herba Potamogetonis Pectinati enzymolysis, the environmental pollution that submerged plant amount reproduction causes can not only be alleviated, solve the handling problems of agricultural wastes, also by the high-valued production green bio energy of organic waste, reduce the dependence to fossil oil to a certain extent, optimize China's energy structure, promote the improvement of socioeconomic Sustainable development and ecotope.
Summary of the invention
For solving above-mentioned problems of the prior art, the invention provides the biological flue gas preparation method of a kind of enzymolysis high microsteping waterplant co-producing hydrogen and methane.The prolific submerged plant that body eutrophication causes by the method salvages transfer, as fermentation substrate after the pre-treatment of employing degrading enzyme enzymolysis, and mix with anaerobic activated sludge, by anaerobe fermentation mode, methane phase after reaction conditions in adjustment reaction process reaches and produces hydrogen, realize hydrogen-methane combination producing, reclaim contained biomass energy in SOLID ORGANIC matter with the form of biological flue gas.The present invention achieves and reduces discharging the target of production capacity while organic waste higher value application, and renewable resources is utilized, Pollution abatement and bioenergy preparation combine and carry out, and has important environmental benefit and wide application prospect.
The preparation method of the biological flue gas of enzymolysis high microsteping waterplant co-producing hydrogen of the present invention and methane:
(1) enzymolysis pre-treatment: high microsteping waterplant is cleaned up postlyophilization, being crushed to particle diameter is 0.2-1cm; Then mixing with degrading enzyme adds in retort, and the mass ratio of degrading enzyme and high microsteping waterplant is (1:1)-(15:1) mg/g; Add the water of 0.5-5 times of volume, temperature 35-55 DEG C, after processing 12-48h under anaerobic condition, it is for subsequent use that taking-up is cooled to room temperature;
(2) in the hydrogen producing stage: add in anaerobic fermentation tank by pretreated for step (1) enzymolysis high microsteping waterplant, the anaerobic activated sludge of access 10-30wt%, passes into nitrogen or argon gas 2-10min, the air in eliminating system; The pH value controlling reaction system is 4.5-6.5, and temperature of reaction is 30-50 DEG C, and stirring velocity controls at 80-180rpm, enters the methane phase stage after producing hydrogen 7-15d;
(3) in the methane phase stage: control ph is 7-8, temperature of reaction is 30-50 DEG C, and stirring velocity is 80-180rpm, termination reaction after methane phase 7-15d.
Described high microsteping waterplant is submerged plant, comprises Herba Potamogetonis Pectinati, eel grass, hornwort, watermifoil, black algae.
Described degrading enzyme is one or more in cellulase, hemicellulase, lignoenzyme; Its cellulase comprises endoglucanase, 1,4-BETA-D-glucancellobio-hydrolase, cellobiase, beta-glucosidase, and lignoenzyme comprises lignin peroxidase, laccase and manganese peroxidase.
Described pH value regulation and control adopt the NaOH solution of HCl and 0.5-2.5M of 0.5-2.5M to add to enter in anaerobic fermentation tank through peristaltic pump stream and control.
Principle of the present invention is that degrading enzyme is adsorbed on the Mierocrystalline cellulose of submerged plant specifically, make natural cellulose under a kind of the unwind factor or the effect of solution hydrogen bond enzyme of non-hydrolytic character, open with intrachain hydrogen bond between cellulose chain, form unordered amorphous cellulose element, cellodextrin and glucose is hydrolyzed into, to improve the utilization ratio of substrate under the synergy of degrading enzyme; Then under anaerobic, utilizing the effect of anaerobic sludge mixed strains to carry out biological fermentation, is first voltaile fatty acid and hydrogen by the organic high molecular compound in submerged plant after enzymolysis, carbohydrate, protein and steatolysis; Second step methane phase stage methanogen utilizes the volatile short chain fatty acids generation methane producing acid phase and generate, and reaches hydrogen-methane coproduction.
Compared with prior art, the invention has the advantages that:
(1) the present invention utilizes highly effective biological zyme to carry out pre-treatment to high fiber vegetable, effective destruction plant wax Rotating fields, increase microorganic adhesion area and biological enzyme reaction interface, improve the specific adsorption effect of biological enzyme and microorganism, significantly improve the capacity efficiency of high fiber vegetable co-producing hydrogen and methane combustion gas, shorten the start time of reactor.
(2) the present invention's a large amount of high fiber vegetable high level energy that water body in lake eutrophication and water remediation are produced, not only make nitrogen in lake, the build-up effect of phosphorus recycling is effectively controlled, reduce biology and fill and lead up effect, and it is cost-saving, reduce solid waste to the harm of environment, achieve the resource utilization of organic waste, minimizing, innoxious.
(3) in the present invention high microsteping waterplant after biological enzymolysis pre-treatment, by regulation and control pH value, organic loading etc., make microorganism Adaptable growth environment in single reaction vessel reaction system, realize two benches anaerobically fermenting production capacity, realize production and the collection of hydrogen and methane stage by stage, its hydrogen product, methane can not cause secondary pollution to environment.
(4) easy handling of the present invention and control, equipment is simple, reaction conditions is gentle, energy consumption is low, efficiency is high, can produce biological flue gas---hydrogen and methane, ensure the microbial metabolism balance of hydrogen production through anaerobic fermentation process while degraded high microsteping waterplant, efficiently solve hydrogen production through anaerobic fermentation efficiency low, produce the problems such as hydrogen process instability.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the biological flue gas preparation method of enzymolysis high microsteping waterplant co-producing hydrogen and methane;
Fig. 2 is the gas-phase product color atlas in embodiment 1 anaerobic fermentation to produce hydrogen stage;
Fig. 3 is the gas-phase product color atlas in embodiment 1 anaerobically fermenting methane phase stage.
Embodiment
Embodiment 1
(1) enzymolysis pre-treatment: the Dominant Submerged Macrophytes Herba Potamogetonis Pectinati of Ulansuhai Nur is cleaned up postlyophilization, being crushed to particle diameter is 0.5-1cm; Then mixing with cellulase R-10 adds in anaerobic fermentation tank, and the mass ratio of cellulase R-10 and Herba Potamogetonis Pectinati is 10mg/g; Add the water of 2 times of volumes, temperature 48 DEG C, after processing 48h under anaerobic condition, it is for subsequent use that taking-up is cooled to room temperature;
(2) in the hydrogen producing stage: add in anaerobic fermentation tank by pretreated for step (1) enzymolysis high microsteping waterplant, the anaerobic activated sludge of access 25wt%, passes into nitrogen 2min, the air in eliminating system; The pH value controlling reaction system is 5.0, and temperature of reaction is 37 DEG C, and stirring velocity controls at 150rpm, enters the methane phase stage after producing hydrogen 7d;
(3) the methane phase stage: regulate pH to 7, temperature of reaction is 37 DEG C, and stirring velocity is 150rpm, termination reaction after methane phase 10d.
Herba Potamogetonis Pectinati used, water ratio is 80%-98%, crude protein 7.55-15.21%, crude fat 0.6-1.89%, crude fibre 19.1-23.7%, and total glucides is containing 46.0-51.6%.
Described pH value regulation and control adopt the NaOH solution of HCl and 1M of 1M to add to enter in anaerobic fermentation tank through peristaltic pump stream and control.
Wherein, collection and confinement of gases adopts exhaust gas collection method, and compound mensuration adopts gas phase-mass spectrometry chromatographic instrument to measure gas phase and liquid product composition, and wet test meter measures gas production rate.
Adopt SP-6890 type gas chromatography determination fermentation gas-phase product composition and concentration, GC conditions is: column length 4m, carrier is 13X molecular sieve, TCD thermal conductivity cell detector, and high-purity argon gas does carrier gas, flow velocity is 40mL/min, column temperature 120 DEG C, thermal conductivity cell and sampler temperature are 150 DEG C, sample size 1mL, with peak area quantification, correct normalization method and calculate gas content.The color atlas of each composition measurement of biogas is see Fig. 2 and 3.
Claims (3)
1. a biological flue gas preparation method for enzymolysis high microsteping waterplant co-producing hydrogen and methane, is characterized in that, its concrete operation step is:
(1) enzymolysis pre-treatment: high microsteping waterplant is cleaned up postlyophilization, being crushed to particle diameter is 0.2-1cm; Then mixing with degrading enzyme adds in retort, and the mass ratio of degrading enzyme and high microsteping waterplant is (1:1)-(15:1) mg/g; Add the water of 0.5-5 times of volume, temperature 35-55 DEG C, after processing 12-48h under anaerobic condition, it is for subsequent use that taking-up is cooled to room temperature;
(2) in the hydrogen producing stage: add in anaerobic fermentation tank by pretreated for step (1) enzymolysis high microsteping waterplant, the anaerobic activated sludge of access 10-30wt%, passes into nitrogen or argon gas 2-10min, the air in eliminating system; The pH value controlling reaction system is 4.5-6.5, and temperature of reaction is 30-50 DEG C, and stirring velocity controls at 80-180rpm, enters the methane phase stage after producing hydrogen 7-15d;
(3) in the methane phase stage: control ph is 7-8, temperature of reaction is 30-50 DEG C, and stirring velocity is 80-180rpm, termination reaction after methane phase 7-15d;
Described degrading enzyme is one or more in cellulase, hemicellulase, lignoenzyme; Its cellulase comprises endoglucanase, 1,4-BETA-D-glucancellobio-hydrolase, cellobiase, beta-glucosidase, and lignoenzyme comprises lignin peroxidase, laccase and manganese peroxidase.
2. preparation method according to claim 1, is characterized in that, described high microsteping waterplant is submerged plant, comprises Herba Potamogetonis Pectinati, eel grass, hornwort, watermifoil, black algae.
3. preparation method according to claim 1, is characterized in that, described pH value regulation and control adopt the NaOH solution of HCl and 0.5-2.5M of 0.5-2.5M to add to enter in anaerobic fermentation tank through peristaltic pump stream and control.
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| CN103757058B (en) * | 2014-01-28 | 2015-09-09 | 福建农林大学 | A kind of method utilizing energy grass and kelp co-fermentation to prepare biological flue gas |
| CN104004653B (en) * | 2014-05-16 | 2016-05-25 | 沈阳航空航天大学 | Anaerobic digestion gas production catalysis methanol loop processed is utilized system |
| CN105177051A (en) * | 2015-09-15 | 2015-12-23 | 中国农业大学 | Method for improving efficiency of producing biogas through anaerobic fermentation by adopting energy grass |
| CN108841580B (en) * | 2018-07-27 | 2021-11-30 | 中国农业大学 | Hydrogen-producing and methane-producing reactor for treating solid waste |
| CN111100835B (en) * | 2020-01-07 | 2021-12-31 | 中国科学院青岛生物能源与过程研究所 | PET degradation biocatalyst and application thereof |
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| CN1896252A (en) * | 2006-06-24 | 2007-01-17 | 中国科学技术大学 | Production of marsh-gas by organic efficient anaerobic fermentation |
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| CN1896252A (en) * | 2006-06-24 | 2007-01-17 | 中国科学技术大学 | Production of marsh-gas by organic efficient anaerobic fermentation |
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| 水生植株残体厌氧发酵产气的研究;秦蓉等;《中国科技论文在线》;20110611;正文第1页至第5页 * |
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